I haven't tried it with PHP, but in theory, you might be able to use the [man]fopen[/man] and its related functions. More specifically for use with *nix (but you'll need to find the system name for the com port (ttyS0, ttyS1, etc - I think). If its Windows, the "datatosend > com1" trick should work. I believe you may be able to open the port with fopen and using "com1" as the file name, but I'm not positive.
Worse comes to worse, a really simple C/C++ app could be created to do it and PHP just calls it.